Catalyst system

ABSTRACT

The present invention relates to a new catalyst system for fluorous biphasic catalysis processes which comprises functionalized polymeric beads, monodisperse SiO 2  or SiO 2  flakes associated with the catalyst. These functionalized particles are used as a support for catalysts in fluorous biphasic catalysis (FBC).

[0001] This invention relates to a new catalyst system for fluorousbiphasic catalysis processes which comprises functionalized plasticbeads, monodisperse SiO₂ or SiO₂ flakes together with the catalyst inthe fluorous phase. These functionalized particles are used as a supportfor catalysts in catalytic processes, especially in fluorous biphasiccatalysis (FBC).

[0002] There is an increasing interest in the development of newliquid-liquid biphasic catalytic systems. One of the most interestingrecent developments in homogeneous catalysis is the concept andapplication of flourous biphase catalysis (FBC, I. T. Horvath and J.Rabai, Science, 1994, 266, 72). The principle of FBC is based on thelimited miscibility of common organic solvents with perfluorinatedcompounds. A very attractive aspect of FBC is that it provides, by meansof phase separation, an elegant solution of the catalyst/productseparation problem associated with homogeneous catalysis. The FBC methodshows appealing general features, such as the employment of nontoxic,reusable perfluorocarbons and the easy separation of the catalyst fromreactants and products. Moreover, the inertness of perfluorocarbons andthe high solubility of oxygen in these fluids would be particularlyhelpful in oxidation reactions.

[0003] Catalytic and stoichiometric reactions can be carried out in thefluorous biphase system, the simplest version being a two-phase mixtureconsisting of a perfluorcarbon (PFC) and a non-fluorinated solvent. Thecatalyst (or one of the reagents) is immobilized in the perfluorocarbonphase while the substrate (or substrates) and the product (or products)are dissolved in the organic solvent. Alternatively it is also possibleto carry out the reaction under homogeneous conditions, by choosing aPFC/organic solvent couple that shows a thermally controlledmiscibility.

[0004] In both cases when the reaction is finished the fluorous phase iseasily recovered through simple phase separation, and can be reusedwithout further treatment in a new reaction cycle.

[0005] The FBC technique is particularly adapted to reactions where theapolar substrates are converted to products of greater polarity, in thatthese are very easily expelled from the fluorous phase. Other positiveaspects of the FBC technique are: the use of non-toxic PFC as a reactionmedium, the lack of chemical coordination with catalysts, i.e. thepossible improvement of the chemical stability of the homogeneouscatalyst due to “site isolation”, and the easy separation of thecatalyst and/or the exhausted reagents form the products. The futuredevelopments of the FBC approach are closely connected to theavailability of efficient catalysts having, simultaneously, highsolubility in the perfluorinated phase and electronic characteristicslike those of analogous products soluble in normal organic solvents.

[0006] Successful application of FBC depends on rational design ofcatalysts that show high affinities to the fluorous phase, that arehighly efficient and easy to prepare. Until now, there are some suitablecatalysts known such as for example flurorous soluble metal catalyststhat are based on molecular metal complexes containing conventionalligands modified with fluorinated groups (see Horvath, Acc. Chem. Res.,1998, 31, 641; or de Wolf et al., Chem. Soc. Rev., 1999, 28, 37). Thebest known such catalysts are perhaps rhodium trialkylphosphinecomplexes appended with fluorous ponytails such as[RhH(CO){P(CH₂CH₂C₆F₁₃)₃}₃]. The applicabilitiy of these complexes hasbeen convincingly demonstrated by Horvath and Gladysz in the fluorousbiphase hydroformylation (see Horvath et al., J. Am. Chem. Soc., 1998,120, 3133), hydrogenation (see Rutherford et al., Catal. Today, 1998,42, 381) and hydroboration (see Juliette et al., J. Am. Chem. Soc.,1999, 121, 2696).

[0007] Further Pozzi et al., prepared among others fluoroustetraarylporphyrin complexes with cobalt and manganese (see Chem.Commun., 1997, 69 and Tetrahedron, 1997, 52, 6145). Further examples offluorous oxidation catalysts are Ru and Ni complexes of the fluorinatedacetylacetonate anion {[(C₇F₁₅)C(O)CHC(O)(C₇F₁₅)]⁻} reported by Klementet al., Angew. Chem. Int. Ed. Engl., 1997 36, 1454.

[0008] A fluorous palladium complex [Pd{P(C₆H₄C₆F₁₃)₃}₄] turned out tobe active in a cross-coupling of arylzinc bromides and aryl iodides(Betzemeier and Knochel, Angew. Int. Ed. Engl., 1997 36, 2623).

[0009] Bergbreiter and Franchina (Chem. Commun, 1997, 1531) describedthe synthesis of a fluorous phase soluble fluorocarbon polymer thatcovalently bind amine-containing reagents and that react with andseparate from reagents in aqueous and hydrocarbon solvents.

[0010] Fluorous soluble polymer ligands have also been prepared andshown to be active and selective catalysts when combined with rhodiumfor the fluorous biphase hydroformylation of various olefins by Chen etal., Chem. Comm., 2000, 839.

[0011] However, the use of perfluorocarbons may have some disadvantages.Well known are the C₁- and C₂-fluorocarbons (freons) which aregreenhouse gases and have become a major environmental problem becauseof their inertness. The higher perfluoroalkanes have lower vaporpressures and might therefore cause less environmental problems thantheir smaller chain analogues. About the impact, however, of longerperfluoroalkanes on the greenhouse effect, less is known. Therefore, itwould be desirable and necessary to reduce the volume of theperfluorocarbons (PFC).

[0012] Furthermore, there is still a great need of suitable catalystsystems that are highly efficient, highly soluble in the fluorous phase,easy to prepare and easily recovered as the future developments of theFBC approach are closely connected to the availability of efficientcatalysts having those advantages.

[0013] Surprisingly it has been found that functionalized plastic beads,monodisperse SiO₂ or SiO₂ flakes together with the catalyst in thefluorous phase are highly suitable as a new catalyst system for fluorousbiphasic catalysis processes and for catalytic processes in general.

[0014] Thus, the subject of the present invention is a new catalystsystem for fluorous biphasic catalysis processes comprisingfunctionalized plastic beads, monodisperse SiO₂ or SiO₂ flakesassociated with the catalyst in the fluorous phase.

[0015] Subject of this invention is also the use of plastic beads,monodisperse SiO₂ or SiO₂ flakes which are functionalized, as a supportmaterial for catalysts in catalytic processes.

[0016] The plastic beads, the monodisperse SiO₂ particles or the SiO₂flakes are initially functionalized to facilitate interaction with thecorresponding catalyst. This allows the chemistry to be performed in athin film of liquid adhering to the surface of the beads or SiO₂particles. As a result, a vastly reduced volume of the fluorinatedsolvent—which is expensive and not environmentally friendly—is requiredwhilst continuing to facilitate a continuous process and to maintain theadvantages of the FBC approach. As mentioned before Bergbreiter andFranchina (Chem. Commun, 1997, 1531) and Chen et al., Chem. Comm., 2000,839 described a similar approach using a fluorous soluble polymercatalyst or a fluorpolymer support for fluorous phase chemistry. Inthese cases the reagent is either covalently bonded (Bergbreiter) oralready contains ligands which only require the introduction of a metal(Xiao). However, in the case of the support material of the presentinvention, the full catalyst (i.e. metal plus ligands) are added later.This allows variations to both the metal and ligands using one supportmaterial.

[0017] Furthermore, the polymeric beads of the present invention have nochemical bond between the support material and the catalyst.

[0018] Unlike the polymers of the prior art, the beads or the SiO₂particles are not soluble in the fluorous layer—they associate with itdue to the functionality on the surface. This decreases the incidence ofemulsion formation when the hydrocarbons and fluorocarbons mix which isa disadvantage of the prior art approach.

[0019] Also, the separation of the plastic beads or the SiO₂ particlesis easily done i.e. by filtration.

[0020] The most important advantage or progress in view of the wholeprior art concerning FBC is the following: due to the large surface areaof the beads and the non-porous silicas the amount of fluorous solventwhich is expensive and may have environmental issues attached, can bevastly reduced as only a film is required on the surface.

[0021] As regards the plastic beads any polymeric beads which show auniform size and have a varying diameter ranging from 2 000 nm to 25 000nm may be used. Preferably plastic beads based on polymers likepolystyrene or a copolymer of polyamide/polyethylene glycol are used.

[0022] The polymers may already have groups like phenylene orsubstituted phenylene attached.

[0023] The following polymer beads are for example commerciallyavailable and preferably used in the present invention:

[0024] These polymers have to be further functionalized according tothis invention.

[0025] Functionalized non-porous SiO₂ flakes and especiallyfunctionalized monodisperse SiO₂ particles are preferably used as thesupport material according to the present invention. The basic silicaparticles are commercially available from Merck KGaA (Darmstadt,Germany), monodisperse SiO₂ particles are known under the tradenameMonospher®.

[0026] Monospher® is uniform-sized spherical silica, in particle sizesin the range of 20 nm to 25 000 nm, preferably of 100 to 1 000 nm. Thespherical silica is solid, non-porous, and free from agglomeration. Thesurface can also be modified to obtain special properties. For examplehydrophobic particles can be prepared or other organic functional groupslike halides, epoxides, amines etc. can be bound to the silicaparticles. These functional groups are available for further chemicalreactions in particular applications.

[0027] In a further preferred embodiment of this invention monodisperseSiO₂ particles are used which have additionally a magnetic layerunderneath the outermost silica layer. In this case the Monospher® iscovered with magnetite and then covered with another silica layer sothat the surface is the same as the original Monospher® surface layerand can be functionalized in the same way.

[0028] These magnetic silica beads are very easily separated fromreactions by applying a magnetic field. Therefore, they may beadvantageously applied here as an aid to catalyst recovery. The magneticmonodisperse SiO₂ particles have a varying diameter ranging from 50 nmto 25 000 nm, preferably from 50 to 1 500 nm.

[0029] The preparation of those magnetic monodisperse SiO₂ particles aredescribed in the patent application DE 196 38 591.1.

[0030] The plastic beads, monodisperse SiO₂ or non-porous SiO₂ flakesare functionalized with

[0031] a) partially fluorinated chains, or

[0032] b) perfluoro chains, or

[0033] c) hydrocarbon chains, or

[0034] d) branched systems containing perfluoro, hydrocarbon orpartially fluorinated chains,

[0035] each having C₁ to C₃₀ atoms, and

[0036] wherein groups like cycloalkyl or aromatic rings—optionally beingsubstituted by one or more fluorine atoms or fluorinated groups—may bepresent.

[0037] Preferably, partially fluorinated or perfluoro chains andbranched systems containing perfluoro, hydrocarbon or partiallyfluorinated chains having 1 to 30 C atoms, preferably 3 to 20 C atoms,are used. The C—F bonds can be anywhere along the chain and at onespecific C atom all the bonds could be C—F or C—H or there could be acombination of C—F and C—H bonds. Also, the branching could occuranywhere along the chain and could vary in length.

[0038] Preferably, groups like e.g. cyclopropyl, cyclobutyl,cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl or aromatic ringswhich further may be substituted, may be present.

[0039] Thus, functionalization groups like —CF₃, —CH₂F, —CHF₂, —C₂F₅,—CH₂CF₃, —C₃F₇, —(CH₂)₂CF₃, —C₄F₉, —(CH₂)₂(CF₂)CF₃, —(CH₂)₃CF₃,—(CH₂)₂(CHF)CF₃, —C₅F₁₁, —(CH₂)₂(CF₂)₂CF₃, —C₆F₁₃, —(CH₂)₂(CF₂)₃CF₃,—(CH₂)₂(CF₂)₄CF₃, —C₇F₁₅, —C₈F₁₅, —(CH₂)₂(CF₂)₅CF₃, —(CH₂)₂(CF₂)₉CF₃,—(CH₂)₃(CF₂)₄CF₃, -(4-F₁₃C₆)—C₆H₄, -(4—C₇F₁₅CH₂O)—C₆H₄,-[4—C₈F₁₇(CH₂)₃O]—C₆H₄, —(CH₂)₂(CF₂)₂(CF₃CF₂CF₂)CF(CF₂)₂CF₃ arepreferred.

[0040] In all these cases of chains and branches the presence ofaromatic and cycloalkyl groups as mentioned above is possible and thesecan be fluorinated, partially fluorinated and non-fluorinated, too.

[0041] It is also possible to functionalize the Monospher® withhydrocarbons. Thus, systems utilising Monospher® functionalized withhydrocarbon chains and a catalyst with perfluoroalkylchains or visaversa could be envisaged. That means that the catalyst may also havehydrocarbon chains as ligands.

[0042] The hydrocarbon chains may be straight or branched,. and they aretherefore preferably methy, ethyl, n-propyl, butyl, pentyl, hexyl,heptyl, octyl, nonyl, i-propyl, sec-butyl, tert.-butyl, i-butyl,1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-methylpentyl,2-methylpentyl, decyl, undecyl or dodecyl, and further also2,2-dimethylpropyl, 1-ethylpropyl, 3-methylpentyl, 4-methylpentyl,1,1-dimethylpropyl, 1,2-dimethylpropyl, 1,1-dimethylbutyl,1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl,2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl,tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl,nonadecyl or eicosyl.

[0043] Preferably, groups like e.g. cyclopropyl, cyclobutyl,cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl or aromatic ringswhich further may be substituted, may be also present in the abovementioned alkyl groups. Preferred groups are for example,2-cyclopentylbutyl, 2-cyclohexylpropyl, 2-phenylpropyl or3-cyclohexylpentyl, 3-phenylpentyl or 2-phenylbutyl. The cycoalkyl oraromatic groups may be further substituted by any groups that do notdisturb the catalytic reactions, preferably substituents like alkylgroups, partially fluorinated groups or perfluoralkyl groups arepresent.

[0044] In a preferred embodiment of this invention the1H,1H,2H,2H-perfluorooctyl-group is used as the functionalization group.

[0045] Another object of this invention is the possibility tofunctionalize the Monospher® with the catalyst itself. Then, there is acovalent chemical bond between the monodisperse SiO₂ and the catalyst.However, this requires the Monospher® to have for example perfluoroalkylchains so that it is fluorous soluble as well as the catalyst attached.

[0046] The catalyst is attached by reacting it with the SiOH (or SiONagroups after reacting with NaH) on the Monosph®er surface.

[0047] The functionalization of the support material occurs according toknown processes following established routes described for example byAnspach et al., in J. Chromatography, 1988, 457,195.

[0048] In general the procedure is carried out by activating the silicasfirst by heating under vacuum to high temperature (e.g. 200° C.), thensuspending the dehydrated silicas in an appropriate solvent (organicsolvent or water), adding an excess of the corresponding silane reagent(for example 1H, 1H,2H,2H-perfluorooctyltriethoxysilane) and heatingunder reflux for several hours until the reaction is completed. Theresultant functionalized silicas are then purified according to commonmethods for separation and purification and finally dried under vacuum.

[0049] The number of surface silanols per gram of material is normallycalculated assuming a true solid densitiy and perfect sphericalgeometry.

[0050] This general way for functionalization is also used to modify theplastic beads.

[0051] A great advantage is that the coating of organic materials on thesilica particles or the plastic beads can be tailored to specificcatalytic systems (i.e. fluorocarbon or hydrocarbon or both, varyingchain length and the functionality the chain contains).

[0052] These functionalized plastic beads or silica particles are thenused as a support material for catalysts in the fluorous phase influorous biphasic catalysis processes. This is also an object of thepresent invention. The functionalized surface of the silicas or theplastic beads allows the catalysts—usually used in these catalyticprocesses—to associate with the support material by an interaction ofthe catalyst ligands and the coating of the silica or plastic beadssupports. In this case there are no permanent chemical bonds and thesupport materials can be used again. The facilitatedchemisorption/physisorption of the catalysts onto the surface of thesupport materials allows the chemistry of the catalysis to be performedin a thin film of liquid adhering to the surface of the silica particlesor the plastic beads. As a result, a vastly reduced volume of thefluorinated solvent is required whilst continuing to facilitate acontinuous process and to maintain the advantages of the FBC approach.

[0053] As this technique could be applied to any catalytic reaction, notonly for the FBC approach, a further object of the present invention isthe use of plastic beads, monodisperse SiO₂ or SiO₂ flakes which arefunctionalized, as a support material for catalysts in catalyticprocesses in general. It is possible for example to use the newcatalytic system in the palladium catalysed Heck reaction.

[0054] And a further object of this invention is especially the use ofplastic beads, monodisperse SiO₂ or SiO₂ flakes which are functionalizedaccording to this invention, as a support agent for catalysts,preferably fluorous catalysts, in fluorous biphasic catalysis (FBC).

[0055] As regards the catalysts, potentially, any catalyst could be usedwhich are suitable for catalytic reactions.

[0056] Preferably, catalysts are used which are suitable for catalyticreactions like catalytic hydroformylation, hydroboration, C—C coupling,epoxidation, oxidation, reduction and alkylation.

[0057] Especially preferred for fluorous biphasic catalysis arecatalysts having a fluorous ponytail containing complex. That means thatthe catalysts in charge are functionalized with one or severalperfluoroalkylgroups to render these catalysts soluble in a fluorousphase. Most often, perfluorohexyl and perfluorooctyl groups are used.

[0058] Such catalysts are for example phosphines having a certain numberof perfluoroalkyl tails (R_(F)) of appropriate length. An alkyl spacercan be interposed between the donor atom and the R_(F) substituents, inorder to shield phosphorus from the strong electron-withdrawing of thelatter. This kind of ligand proved to be very efficient influorous-organic catalytic reactions such as the hydroformylation ofalkenes (Horvath et al., J. Am. Chem. Soc. 1998, 120, 3133). Othercatalysts are for example fluorous tetraarylporphyrin complexes withcobalt and manganese, Ru and Ni complexes of the fluorinatedacetylacetonate anion {[(C₇F₁₅)C(O)CHC(O)(C₇F₁₅)]⁻}, or a fluorouspalladium complex [Pd{P(C₆H₄C₆F₁₃)₃}₄],

[0059] The known and preferred catalysts for the FBC approach given inthe following are intended only as examples:

[0060] IrH(CO)[P(CH₂CH₂C₆F₁₃)₃]₃,

[0061] IrCl(CO)[P(PhC₆F₁₃)₃]₂,

[0062] RhH(CO)[P(CH₂CH₂C₆F₁₃)₃]₃,

[0063] RhCl[PCH₂CH₂(CF₂)_(n)CF₃)₃]₃ where n=5 or 7,

[0064] Rh(H₂)Cl[PCH₂CH₂(CF₂)_(n)CF₃)₃]₃ where n=5 or 7,

[0065] [RhCl(CO)(P(C₂H₄C₆F₁₃)₃)₂],

[0066] [Pd{(4-F₁₃C₆C₆H₄)₂PCH₂CH₂P(C₆H₄C₆F₁₃-4)₂}₂] and

[0067] [{RhCl{(4-F₁₃C₆C₆H₄)₂PCH₂CH₂P(C₆H₄C₆F₁₃-4)₂]}₂].

[0068] These catalysts are preferably used in the present invention.

[0069] The perfluorinated solvents are preferably chosen from the groupconsisting of perfluoroalkanes, perfluoroalkene, perfluoroethers or—amines, such as for example n—C₆F₁₄, CBF₁₇Br,1,3-dimethylperfluorocyclohexane, perfluormethylcyclohexane orperfluordimethylether.

[0070] As the organic solvent the typical organic solvents normally usedin organic chemistry may be chosen. Preferred solvents are for examplehexane, toluene, benzene, alcohols, dimethylsulfoxide or ethers liketetrahydrofuran.

[0071] The new catalyst system is prepared by mixing the functionalizedsupport material with a suitable catalyst dissolved in a perfluorcarbon.The ratio R of the functionalized support material to the catalyst isusually in the range of R=1.0 to 10.0. Especially preferred is the ratioR=5.0.

[0072] Once the catalyst is associated with the support material (afterstirring for several hours) it can be used immediately for the desiredcatalytic process or may be filtered off and isolated for use with adifferent system or at a later date.

[0073] With the new catalyst system according to this invention there isa new approach available to optimize catalytic processes based on theprinciples of the fluorous biphasic catalysis.

[0074] The use of the functionalized plastic beads or nonporous silicasas a support material for the corresponding catalyst has the followingadvantages.

[0075] The functionalization of the beads or SiO₂ particles facilitatesthe interaction with the perfluoro groups of the corresponding catalystand the chemistry of the catalysis is performed in a thin film of liquidadhering to the surface of the beads or SiO₂ particles. As a result, avastly reduced volume of the fluorinated solvent—which is expensive andnot environmentally friendly—is required whilst continuing to facilitatea continuous process and to maintain the advantages of the FBC approach.Furthermore, the amount of catalyst leaching in the non-fluorous phaseis highly reduced as a result of the very good interaction between thesupport material and the catalyst. The distribution of the fluorouscatalyst in the two phases is also important from an economic point ofview. A fluorous catalyst might be more expensive than a non-fluorous,however, if the catalyst can be fully recovered and is not leaching inthe non-fluorous solvent—and that is the case in the present catalystsystem—it will be cheaper in the long term.

[0076] Especially in case of the magnetic Monosphers®) the recovery isvery easy and efficient.

[0077] A further advantage is that there is a broad variety of differentcatalyst systems available. The coating (functionalization) of thesupport materials can be tailored to specific catalytic systems. Theproduct preparation is simple and uses technologies known to thoseskilled in the art. The support materials could be functionalized withpartially fluorinated chains, perfluoro chains, hydrocarbon chains, orbranched systems containing perfluoro, hydrocarbon or partiallyfluorinated chains as described above.

[0078] The ligand on the catalyst could also have hydrocarbon groups,that means systems utilising Monospher® functionalized with hydrocarbonchains and a catalyst with perfluoroalkylchains or systems utilisingMonospher® functionalized with partially, fluorinated or perfluorinatedgroups and a catalyst with hydrocarbon chains or partially fluorinatedgroups could be envisaged.

[0079] Thus, there are many possibilities and the catalytic system canbe adapted to specific catalytic processes.

[0080] Furthermore, this technique may be applied to any catalyticreaction like catalytic hydroformylation, hydroboration, C—C coupling,epoxidation, oxidation, reduction and alkylation and others.

[0081] From the foregoing description, one skilled in the art can easilyascertain the essential characteristics of this invention and, withoutdeparting from the spirit and scope thereof, can make various changesand modifications of the invention to adapt it to various usages andconditions.

[0082] The entire disclosure of all applications, patents andpublications, cited above and below are hereby incorporated byreference.

[0083] The following examples shall illustrate the present invention.

EXAMPLES

[0084] A) Functionalization of Monospher®

[0085] The Monospher® (250 nm diameter, from Merck KGaA, Darmstadt,Germany) was activated by heating under vacuum to 200° C. The Monspher®was then loaded with an excess of 1H, 1H, 2H,2H-perfluorooctyltriethoxysilane into flame dried glass ware underdinitrogen and refluxed in dry hexane for 72 hours.

[0086] The resultant functionalized monospher (FM) was purified bystirring in a mixture of toluene and 1,3-dimethylperfluorocyclohexane(PP3). On separation the organic layer was decanted off, the fluorouslayer filtered and the residue washed with large amounts of hexane. Thefunctionalized monospher was dried unter vacuum for a further 36 hoursand weighed. The increase in mass suggested around 45% coverage.

[0087] B) Testing the Preference for Fluorous Solvents

[0088] Table 1 shows the results of experiments testing the preferenceof functionalized monospher® (FM) in comparison to unmodified Monospher®in a variety of biphasic systems. TABLE 1 Biphase FM Monospher ®PP3/CH₂Cl₂ PP3 CH₂Cl₂ PP3/C₆H₅CH₃ PP3 C₆H₅CH₃ PP3/MeOH PP3 MeOHPP3/C₆H₅F PP3 C₆H₅F C₆H₅CH₃/H₂O C₆H₅CH₃ H₂O

[0089] The perfluoroalkyl functionalized monospher showed a clearpreference for highly fluorous solvents.

[0090] C) Preparation of a Catalyst System According to the Invention

[0091] The functionalized monospher prepared in example A) was used as asupport for a fluorous ponytail containing complex. 50 mg of the highlycolored, fluorous soluble IrCl(CO)[P(PhC₆F₁₃)₃]₂ was dissolved in1,3-dimethylperfluorocyclohexane and added to an equal weight offunctionalized monospher in a 100 ml flask. The mixture was stirred for3 hours. Then the catalyst is associated with the support material andcan be filtered off, isolated and used as for any catalytic process.

1. New catalyst system for fluorous biphasic catalysis processescomprising functionalized plastic beads, monodisperse SiO₂ or SiO₂flakes together with the catalyst in the fluorous phase.
 2. Systemaccording to claim 1 characterized in that the monodisperse SiO₂particles have additionally a magnetic layer underneath the outermostsilica layer.
 3. System according to claim 1 characterized in that themonodisperse SiO₂ particles have a varying diameter ranging from 20 nmto 25 000 nm.
 4. System according to claim 2 characterized in that themagnetic monodisperse SiO₂ particles have a varying diameter rangingfrom 50 nm to 25 000 nm.
 5. System according to claim 1 characterized inthat the plastic beads are polymers like polystyrene or a copolymer ofpolyamide/polyethylene glycol.
 6. System according to claim 5characterized in that the polymers may already have attached groups likephenylene or substituted phenylene.
 7. System according to claim 5 or 6characterized in that the polymer beads have a varying diameter rangingfrom 2 000 nm to 25 000 nm.
 8. System according to at least one of theclaims 1 to 7 characterized in that the plastic beads, monodisperse SiO₂or SiO₂ flakes are functionalized with a) partially fluorinated chains,or b) perfluoro chains, or c) hydrocarbon chains, or d) branched systemscontaining perfluoro, hydrocarbon or partially fluorinated chains, eachhaving C₁ to C₃₀ atoms, and wherein groups like cycloalkyl or aromaticrings—optionally being substituted by one or more fluorine atoms orfluorinated groups—may be present.
 9. System according to claim 1 or 2characterized in that the monodisperse SiO₂ or SiO₂ flakes, preferablyhaving already perfluoro or partially fluorinated groups on the surface,are then functionalized with the catalyst itself.
 10. System accordingto claim 1 characterized in that a catalyst is used which is commonlyknown to be suitable for catalytic reactions and which is preferablysoluble in the fluorous phase.
 11. System according to claim 10,characterized in that a catalyst is used which is suitable for catalyticreactions like catalytic hydroformylation, hydroboration, C—C coupling,epoxidation, oxidation, reduction and alkylation.
 12. System accordingto claim 1 characterized in that the catalyst is a fluorous ponytailcontaining complex.
 13. System according to claim 12 characterized inthat the fluorous catalyst is selected from the group consisting ofIrCl(CO)[P(PhC₆F₁₃)₃]₂, RhH(CO)[P(CH₂CH₂C₆F₁₃)₃]₃,RhCl[PCH₂CH₂(CF₂)(CF₃)₃]₃ where n=5 or 7,Rh(H₂)Cl[PCH₂CH₂(CF₂)_(n)CF₃)₃]₃ where n=5 or 7,[RhCl(CO)(P(C₂H₄C₆F₁₃)₃)₂], [Pd{(4-F₁₃C₆C₆H₄)₂PCH₂CH₂P(C₆H₄C₆F₁₃-4)₂}₂]and [{RhCl{(4-F₁₃C₆C₆H₄)₂PCH₂CH₂P(C₆H₄C₆F₁₃-4)₂]}₂].
 14. The use ofplastic beads, monodisperse SiO₂ or SiO₂ flakes which arefunctionalized, as a support agent for catalysts, preferably fluorouscatalysts, in fluorous biphasic catalysis (FBC).
 15. Use according toclaim 14 characterized in that the plastic beads, monodisperse SiO₂ orSiO₂ flakes are functionalized with a) partially fluorinated chains, orb) perfluoro chains, or c) hydrocarbon chains, or d) branched systemscontaining perfluoro, hydrocarbon or partially fluorinated chains, eachhaving C₁ to C₃₀ atoms, and wherein groups like cycloalkyl or aromaticrings—optionally being substituted by one or more fluorine atoms orfluorinated groups—may be present.